Electronic dynamics in long linear and cyclic polyynes towards the carbyne limit

Abstract

Carbyne-the one-dimensional sp-hybridised allotrope of carbon-has long been predicted to exhibit unique properties, yet its synthesis remains elusive. To probe its behaviour, finite sp-carbon chains such as cumulenes and polyynes have been studied, but work to date has focused almost exclusively on short, linear systems far from the infinite carbyne limit and without considering topology. Here, we investigate long (48-carbon) linear and cyclic polyynes using steady-state and ultrafast, temperature- and polarization-resolved optical and vibrational spectroscopy. We find highly delocalized ground states in both topologies, with Peierls distortions markedly weaker than in short chains. In contrast, excited states undergo rapid self-localisation, with the localisation pathway and subsequent intersystem crossing strongly dependent on chain length and topology. Unlike shorter polyynes, excited-state structural rearrangements are minimal, and comparison with theoretical predictions shows that properties, such as Huang-Rhys factors, have plateaued by 48 carbons. Our results reveal how topology influences the electronic dynamics of long polyynes and refines our understanding of sp-carbon systems approaching the carbyne limit